CN104689598A - Pressurized low polarity water extraction apparatus and methods of use - Google Patents

Abstract

An apparatus for extraction and recovery of components from biomass feedstocks with pressurized low polarity water. The apparatus is configured with two or more reaction columns, each separately communicating with sources of pressurized water, pressurized heated water, and pressurized cooling water. Components are extracted from the biomass by separately flooding the column with pressurized water, heating the column and its contents to the point where the water becomes pressurized low polarity (PLP) water, recovering the PLP water comprising the extracted components, cooling the column with PLP water, and removing the spent biomass material from the column.

Description

Add and force down polar water extraction element and using method

Technical field

Generally speaking, each embodiment disclosed in this invention relates to unit for extraction components from biomass material and system.More specifically, the present invention relates to and force down polar water as the unit of solvent extraction components from biomass material and system for generation of with using to add.

Background

Phytochemical naturally produces in plant and especially causes color as the chemical compound of the darkviolet of blueberry and the garlicky smell of organ sensation performance.Some phytochemical are used to usually sell with medicine type and in the health product usually had nothing to do with food.

The phytochemical of special concern has three classes, i.e. Polyphenols, special carbohydrate and glucosides.Polyphenols (also referred to as phenols) is the compound mainly playing antioxidant and antiphlogistic effect when the mankind take in.Antioxidant is the molecule of the oxidation suppressing other molecules.Oxidation in active somatic cell can cause cytoclasis or death.Antioxidant is by autoxidation, instead of cellular component is oxidized and prevents this destruction.Antioxidant is widely used in dietary supplements, and research finds especially can prevent disorders such as cancers, coronary heart disease, altitude sickness.They are also used as the anticorrisive agent in foods and cosmetics.Neutralize in plant used in the traditional medicine of several culture because antioxidant is present in the food that human diet consumes, its effect in human health and disease is the theme of much research.Polyphenol can commercial synthesis, but obtains primarily of plant and microorganism.

Carbohydrate is in live body, play multifunctional carbohydrate perhaps.Carbohydrate is used as the energy source (such as starch and glycogen) of health and structural constituent (chitin in the cellulose in such as plant and fungi and arthropod).Short-chain carbohydrates is also referred to as sugar, and long-chain or complex carbohydrates are called polysaccharide or oligosaccharides.Carbohydrate and especially can being played a crucial role in immune system, fertilization, prevent disease or infection, blood coagulation by its other derivative compounds.

The sugar that is combined with another functional molecules sugar of phenols bonding (such as with) is called glucosides.Glucosides plays a part many important in live body.Many plants store chemicals with the form of nonactive glucosides.These activate by hydrolysis, and this causes sugar moieties to disconnect, thus make to utilize this chemicals.Such plant glucosides many are used as medicine.

Existing plant component extracting method be with an organic solvent or uninflated hot water to make these component solvent and take out these components from plant biomass.Organic solvent system to use in ethanol, methyl alcohol, ethyl acetate and acetone one or more usually.But the application of organic solvent normally poisonous and its business needs to have authenticated for poisonous and the storage of ignition control compound and the equipment of process explosion-protection equipment.In addition, solvent can be used as unsound trace compound and remains in end product, and its toxicity can cause the safety worries of human consumption.

Be well known that, hot water system is often effective not as organic solvent based systems, and only can extract the potential available phytochemical of a part from plant biomass.

Except health food, living beings can be the valuable source of chemical products.Lignin fiber cellulosic biomass is a kind of material the abundantest in the world and it obtains significant concern as the purposes of producing energy and chemicals raw material.The classification of lignin fiber living beings is realized to improve the utilization that its cellulose, hemicellulose and lignin are formed component by using various physics, biology, heat or chemical method.Hydrothermal treatment consists (also referred to as from hydrolysis, hydro-thermal degraded) comprises steam blasting, adds and forces down polar water (PLPW; Usually also referred to as superheated water, subcritical water, pressurized hot water, compressed hot water), add and force down polar water and make use of the catalytic action of the hydrogen ion of the water ion caused due to treatment conditions and form original position acid (acetic acid such as produced by acetyl group) with the carbohydrate in hydrolyzing biomass.The temperature heated water under elevated pressure higher than its boiling point causes its key property as the change of pH value and polarity, and its dielectric constant is reduced to the value of the dielectric constant (as illustrated in ethanol and methyl alcohol those) close to solvent.

Use batch process and continuous throughflow type system (utilizing hydro-thermal water treatment) to process the lignin-cellulose material of wide region in the system of minimum volume, the hardwood comprised available from eucalyptus, white poplar, Leucaen, maple, Chinese sweet gum is considered to be worth doing, available from vegetable material and the stalk of annual plant, especially comprise wheat stalk, Barley straw, rye stalk, oat straw, Brassica genus stalk, flax-waste, Chinese sorghum, switchgrass, sugarcane.It is known that the products collection efficiency of throughflow type hydrothermal treatment consists with produce in batch system those differ very big.Throughflow type reactor has demonstrated and has taken out than more hemicellulose and lignin in batch system, and forms less catabolite.Can be close to through-flow system and fully take out hemicellulose, and in batch system, only take out 60% (Lui etc., 2002, The Effect of Flow Rateof Compressed Hot Water on Xylan, Lignin, and Total Mass Removalfrom Corn Stover.Ind.Eng.Chem.Res.2003 (42): 5409-5416).In addition, lignin extraction efficiency in batch reactor is less than 30%, but lignin (Lui etc. up to 75% can be taken out with high flow rate in through-flow system, 2003), in addition, the hemicellulose reclaimed in throughflow type reactor is mostly in oligosaccharides form (Lui etc., 2003).

But, owing to realizing with in large extraction vessel and maintaining high pressure to provide constant pressure and temperature and the problem keeping constant raw material throughput relevant simultaneously, still successfully little laboratory system can not be amplified to coml large volume throughput system.Usually the problem run in this amplification is attempted comprises material agglomeration, generation fluid channel (channelling), material channel blocking and back mixing, compared with the result obtained with little laboratory scale equipment, this causes heterogeneous body extract and significantly reduce extraction efficiency.

Invention summary

The present invention relates to for generation of adding the device that forces down polarity (PLP) water and extracting from biomass material and reclaiming the purposes in component.Exemplary adding, is forced down polar water (PLPW) extraction element and is configured to have two or more reaction towers, and each tower is communicated with pressurized water source, pressurized heat water source and the cooling water source that pressurizes respectively.After biomass material is loaded in reaction tower, extract from biological material with five one step process in each tower and to reclaim in biological material contained component, described method comprise make four strands independently current flow through each tower.First in the first tower, load fresh biomass material and provide energy to described device.After energy provides end, described method comprises first step with pressure (hydraulic) water liquid flooding (flooding) this tower, heats the second step of this tower and content thereof, in this tower, take out the 5th step of useless biological material with the third step of PLP water-treatment biological material, the 4th step cooling this tower by cold pressurised water and this tower emptying.And then fresh biomass material is filled with in this tower.During third step, from this tower, collect the water comprising extraction components with the form of one or more decile material, i.e. liquid product stream.

Brief description

With reference to following Figure, the present invention is set forth, in the drawing:

Fig. 1 is indicative flowchart, which show exemplifyingly to add the operation forcing down polar water (PLPW) extraction system, and described system uses five Tower Systems with four strands of independent process streams;

Fig. 2 is the schematic diagram of the exemplary five tower PLPW systems of Fig. 1;

Fig. 2 A is the close up view of the 2A part of Fig. 2;

Fig. 3 is the schematic diagram of the exemplary liquid flooding stream of five tower PLPW systems shown in Fig. 2;

Fig. 4 is the exemplary schematic diagram adding hot-fluid of five tower PLPW systems shown in Fig. 2;

Fig. 5 is the schematic diagram of the exemplary process flow of five tower PLPW systems shown in Fig. 2;

Fig. 6 is the schematic diagram of the exemplary cool stream of five tower PLPW systems shown in Fig. 2;

Fig. 7 is the indicative flowchart of another exemplary PLPW method of the present invention, and it uses five Tower Systems with three strands of independent process streams;

Fig. 8 is the schematic diagram of exemplary 2 tower pilot-scale PLPW systems;

Fig. 9 is the schematic diagram of exemplary stage scale PLPW system;

Figure 10 is the schematic diagram of exemplary amplification PLPW system;

Figure 11 (A)-11 (C) for showing in the PLPW system of the pilot plant scale shown in Figure 10 after PLPW process wheat stalk, the figure that cellulose (11 (A)), hemicellulose (11 (B)) and lignin (11 (C)) distribute in reaction tower;

Figure 12 (A) is for compared for by the figure reclaiming carbohydrate extract in bench scale reaction tower, iodine tower and pilot-scale reaction tower with PLPW process wheat stalk, and Figure 12 (B) is for compared for the figure being reclaimed non-carbohydrate extract during same process round by three towers;

Figure 13 (A)-13 (C) shows by the cellulose (13 (A)), hemicellulose (13 (B)) and lignin (13 (the C)) productive rate that use the PLPW process of iodine tower and pilot-scale reaction tower to obtain;

Figure 14 (A) and 14 (B) is with the chromatogram under the 280nm (14 (A)) of bench scale PLPW system process Concord grape skin and 520nm (14 (B));

Figure 15 shows the chromatogram processed by pilot-scale PLPW system " the long round of C2 on February 1 " under 280nm and 520nm of Concord grape skin (see table 12);

Figure 16 (A) and 16 (B) is with the chromatogram under the 280nm (16 (A)) of bench scale PLPW system process mossberry skin slag and 520nm (16 (B));

Figure 17 (A) and 17 (B) is with the chromatogram under the 280nm (16 (A)) of pilot-scale PLPW system process mossberry skin slag and 520nm (16 (B));

Figure 18 (A) and 18 (B) is commercially available apiin standard specimen (18 (A)) and the chromatogram ground under the 270nm of parsley got by MeOH-water extraction;

Figure 19 (A)-19 (C) is at 110 DEG C (Figure 19 A)), the chromatogram analyzed of PLPW extracts parsley under 120 DEG C (Figure 19 (C)) and 130 DEG C (Figure 19 (C)) HPLC;

Figure 20 is using 30mL/g solvent for showing: the figure of the accumulation dry productive rate extracted from root of Rhodiola sachalinensis living beings (the dry initial substance of 14.49g) in the PLPW system of solid ratio;

Figure 21 (A)-21 (C) is Luo Saiyin (rosarin), network plug dimension (rosavin), the representative chromatogram of 100 μ g/mL standard specimens under 250nm (Figure 21 (A)) and 276nm (Figure 21 (B)) of rosin and rhodioside and SIM holotype electrospray ionization mass spectrum figure (Figure 21 (C));

Figure 22 (A)-22 (C) is dry PLPW gadol extract, representative chromatogram under 250nm (Figure 22 (A)), 276nm (Figure 22 (B)) of 10mg/mL (70% methyl alcohol) solution of 110 DEG C of temperature fractions 1 and SIM holotype electrospray ionization mass spectrum (Figure 22 (C)); With

The 10mg/mL (70% methyl alcohol) that Figure 23 (A)-23 (C) is reference root of Rhodiola sachalinensis biomass extract is at 250nm (the representative chromatogram under Figure 23 (A), 276nm (Figure 23 (B)) and SIM holotype electrospray ionization mass spectrum (Figure 23 (C)).

Detailed Description Of The Invention

Exemplary of the present invention relates to for generation of adding the device that forces down polarity (PLP) water and extracting from biomass material and reclaiming the purposes in component.

From biomass material, add the exemplary semicontinuous method forcing down polar water (PLPW) extraction and reclaim component be shown in the Fig. 1 using the exemplary PLPW device shown in Fig. 2, wherein said PLPW device comprises 5 extraction/reaction towers be arranged in parallel.Generally speaking, presetting water saving is forced into about 750psi by described PLPW method, then the temperature of described pressure (hydraulic) water is risen to about 180 DEG C, then makes the water of this heating and pressurization by selected reaction tower with extraction components from raw material.With regard to flow velocity, described exemplary PLPW device ability is about 30L/ minute for about 2-, about 4-is about 20L/ minute, about 6-is about 15L/ minute, about 8-is about 12L/ minute, about 10L/ minute.In order to contribute to economical operation, described exemplary PLPW device can run with semicontinuous method, and one of them reaction tower is in treatment state always, and from this system, obtain continuous print PLPW extract flow.

The control program of the PLPW method shown in Fig. 1 and the PLPW device shown in Fig. 2 can partial automation, and can comprise Non-follow control processing sequence.In one embodiment, operator must use hand push button to start each process section.Once start, then this system can needed for institute's selections, automatically running/arrestment, complete valve and drive and monitor critical equipment.Described control program can be carried out automatically based on the error detection (to guarantee that this equipment safety runs) of the sequential of various processes and measuring instrument.

Method and apparatus describes:

PLPW device shown in Fig. 2 comprises four bursts of independently process flow, and its control PLPW is by the flowing of each reaction tower.The flowing stream of each reaction tower is selected by the automation control system of the valve operation order controlled in each reaction tower stream.Term " heater " is used in reference to the equipment for PROCESS FOR TREATMENT water, and contains " immersion heater " and " shell and tube exchanger " that can be connected with factory steam system.

hot branch road stream:

In the first process flow, the remainder of each reaction tower stream and PLPW system is isolated, and pump drives water to flow through from cistern: the input side of (i) First Heat Exchanger, (ii) heater, (iii) outlet side of First Heat Exchanger, (iv) back pressure regulator, (v) second heat exchanger, enters (vi) waste water container subsequently.The object of hot branch road stream is that pressurization is keeping system pressure also before PLP water introduces other streams, and adjustment adds the temperature forcing down polarity (PLP) water.This stream flows with process and shares described equipment.

liquid flooding stream:

With lower than the reaction tower being filled with biomass material to be extracted selected by the hot water liquid flooding of 100 DEG C, then pressurize.This task can complete in one of at least two kinds of modes.First method uses independently liquid flooding stream, and wherein pump drives water from cistern by heater, back pressure regulator being expelled in waste water container from this system.This option allows to control liquid flooding coolant-temperature gage better.

Second method uses cool stream (Fig. 6), and this will hereafter describe in more detail.Second method comprises to be made PLP water be diverted to from back pressure regulator to treat in the reaction tower of liquid flooding.Second back pressure regulator makes this tower pressurize.The advantage of the second liquid flooding method is that minimizing completes the tower pressurization necessary equipment of task (extra pump and heater), allows thus: (i) is by more water recycle, and (ii) reclaims extra product extract.Shortcoming is that the temperature of liquid flooding water is lower than the temperature (60 DEG C or if possible, lower) of independent stream and multiple tower must be filled with biomass material when processing and starting day before treatment.

add hot-fluid:

Adding in hot-fluid (Fig. 4), PLP current are through tower chuck, then flow through: the input side of (i) First Heat Exchanger, (ii) heater, (iii) tower chuck, the outlet side of First Heat Exchanger, (iv) back pressure regulator 250, (v) second heat exchanger 260, and be expelled to from this system in the first cistern 110.Add hot-fluid 200 and additionally comprise bypass valve 245 tower 10,20,30,40,50 and the described hot-fluid that adds to be separated.

The object adding hot-fluid is that tower to be heated to selected desired treatment temp minimum to be down to from PLP water to the thermal loss of described equipment during making extraction.Optionally will add hot-fluid and other stream separates, thus it is run independently by increasing pump, heat exchanger and be exclusively used in the heat exchanger that adds hot-fluid.Or, steam in order to being used for from treatment facility can be set to reaction tower chuck, itself otherwise use steam as the heat medium in chuck, or use heat exchanger and water pump to use the water of steam indirect tower chuck.

process stream:

In process stream 300 (Fig. 5), pump 320 drives water from the input side of the second cistern 210 by heat exchanger 330, then by heat exchanger 340, PLP water (under the pressure of pump 320) flows through one of tower 10,20,30,40,50 being filled with biomass material to be extracted subsequently.Described PLP water flows out through the outlet side of heat exchanger 330 from described tower, by back pressure regulator 350, and the second heat exchanger 360, and flow out in collection container 380 from this system.Process stream 300 additionally comprises bypass valve 345 tower 10,20,30,40,50 and described process stream to be separated.The object of process stream (Fig. 5) makes the interested compound solventization of described raw material and therefrom extracts.Described PLP water from bottom to top one-way stream through described reaction tower.First the water that concentration is minimum flow through maximum extraction raw materials, makes the product amount extracted maximize thus.In addition, continue to flow through this characteristic due to described extraction system, with constant taking-up product from this system of the low time of staying when shelves are exposed under operating condition, reduce potential product degradation amount thus.

cool stream:

After raw material fully extracts in two steps, last process stream, namely reaction tower cools by cool stream 400 (Fig. 6).In cool stream 400, described PLP current are through being filled with the reaction tower of the raw material through extracting, and pump 420 drives water to pass through the input side of heat exchanger 430 thus, by a back pressure regulator, and flows out to outlet from this system.The object of the second step of described cool stream is the level by being brought down below saturation temperature through the raw material of extraction and the temperature of reaction tower, thus can take out safely the raw material through extracting.Once temperature is enough low, then this systematic evaluation can be back to the first cool stream, and this tower can emptied of water, take out through extract raw material and add fresh material to carry out extraction round next time.

emptying/to reload:

After described extraction process terminates, before reaction tower can unload treated biomass material, water outlet side by side of the reactor of pressurization must being reduced pressure.Optional biomass material is loaded into one or more insertion for the treatment of reaction tower in sleeve in, from reaction tower, take out sleeve subsequently, and living beings remove from sleeve.Or, directly living beings can be loaded in reaction tower and also therefrom reclaim after treatment.Optionally provide compressed air supplies or water source of supply or steam source of supply to be displaced from reaction tower by useless biomass material, thus contribute to its unloading.

It is to be noted, if desired, four strands optionally included by described five reaction tower devices independent streams, namely liquid flooding stream (Fig. 3), add hot-fluid (Fig. 4), process stream (Fig. 5), cool stream (Fig. 6) be reduced to three strands of independent streams by following measure: (i) cancels liquid flooding stream, (ii) use cool stream to provide liquid flooding stream and cool stream, as shown in Figure 7.

Fig. 8 shows another exemplary PLPW device 700, wherein tower 720 of comprising two reaction towers, 721 maximum operating pressures under the operating temperature of 204 DEG C with 6200kPa (900psi).Tower chuck is designed for the lower maximum operating pressure of 2,580kPa (375psi) under the operating temperature of 204 DEG C, if tower when tower does not pressurize to prevent chuck from pressurizeing is broken.But, due to other equipment of pieces, as accumulator (accumulator) 725,726 authenticatedly can be used for lower than tower 720,721 those temperature and pressures, the maximum operating pressure of this double tower system and temperature are set in 5500kPa (800psi) and 180 DEG C on the whole, and the maximum operating pressure of chuck stream 750 is 2400kPa (350psi).The specification of the PLPW system critical piece shown in Fig. 8 and description are listed in table 1-6.

For this, to add the process flow 718 forcing down polar water extraction system shown in Figure 8.From cistern 710, take out fresh water (FW) with positive-dispacement pump 712 (established technology process pump), and make it by heat exchanger 714, herein, described fresh water (FW) is first for cooling and reclaim heat from the liquid extract of discharging this system.Then, the water of this part heating enters in immersion heater 716, is heated to required technological temperature herein.Control this system to lead the water of described heating through tower chuck to heat this equipment, or lead the tower 720 through being filled with raw material to be extracted.Liquid extract/the fresh water (FW) of discharging, back up through heat exchanger 714, recovers energy herein and before arrival back pressure regulator 751, product temperatur is brought down below boiling point.The object of back pressure regulator 751 system pressure is remained on point higher than the saturation pressure run under treatment temperature to prevent from forming steam.

Table 1:

* length=bed degree of depth

* the time of staying=the bed degree of depth/apparent speed

* * extraction time=volume/flow rate of collection

Table 2: the electrical equipment of double tower PLPW device

Table 3: for the valve of double tower PLPW device

Table 4: for the heat exchanger of double tower PLPW device

Table 5: for mechanically-operated controller and the safety valve of double tower PLPW device

Table 6: the instrument of double tower PLPW device

In the system.After back pressure regulator 751, there is extra heat exchanger 730, it can be used for the final temperature controlling the liquid extract/fresh water (FW) of discharging.This heat exchanger 730 is connected with another water source, and described stream is by valve regulated thus, thus by the liquid cools of discharge to required temperature.Described liquid extract/fresh water (FW) is directed in collection container 732 or waste water container 734 local for other of described technique.

The dynamic stream of number plume is there is in described extraction system.Select described flowing stream with automation control system, described Systematical control valve order is to operate each plume.

hot branch road stream:

Described hot branch road stream by reaction tower 720,721 and the remainder of chuck and PLPW device separate.Process pump 712 make water from cistern 710 by heat exchanger 714 (input side), immersion heater 716, by bypass valve BVH, heat exchanger 714 (product side), back pressure regulator 751, heat exchanger 730 being expelled in waste water container 734 from this system.The object of hot branch road stream is pressurizeed and maintains system pressure, and regulated the temperature of this water before fresh water (FW) is introduced in other streams.

add hot-fluid:

Adding hot-fluid drives water by reaction tower chuck.Process pump 712 drives water to pass through the outlet side of the input side of heat exchanger 714, immersion heater 716, tower chuck, heat exchanger 714, by LPV and back pressure regulator 753, heat exchanger 730, and is expelled in waste water container 734 from this system.The object of this stream is that tower 720 is heated to required treatment temperature, thus makes during milking to be down to minimum from processing the thermal loss of water to equipment.It is pointed out that this stream can separate with other stream and run independently.This realizes by increasing another pump (not shown), heat exchanger (not shown) and immersion heater (not shown).Or described chuck can be transformed into the steam utilized from public utility, itself or use steam as the heat medium in chuck, or pass through to use heat exchanger and water pump with indirect chuck water.

process:

In process stream, fresh water (FW) flows through the reaction tower (such as 720 or 721) being filled with biomass material.Process pump 712 drives water to pass through the input side of heat exchanger 714, immersion heater 716, tower 720 or 721, the product side of heat exchanger 714, back pressure regulator 731, heat exchanger 730, and is expelled in collection container 732 from this PLPW device.The object of process stream is solvation and extracts component contained in biomass material.Described PLP water passes through reaction tower 720 or 721 to its top with one way from bottom it.The minimum water of concentration, first by the denseest raw material, makes extracted product amount maximize thus.In addition, continuing to flow through characteristic due to described extraction system, when being exposed under operating condition with constant taking-up product from described system of the low time of staying, thus reducing potential degradation amount.

cool stream:

After biomass material is fully extracted, cool stream is by reaction tower 720, and 721 cool.The water of the first cool stream 740 takes from cistern 710 or waste water container 734, be pumped across input side, the bypass valve BVC of heat exchanger 744 by coolant pump 742, and pass back through the product side of heat exchanger 744, back pressure regulator 745 be expelled to outlet from PLPW device.The object of the first cool stream 740 to be pressurizeed and the system pressure maintained in cool stream equals extraction column pressure.

In the second cool stream, described PLP current through be filled with useless (namely, through what extract) tower 720 or 721 of biomass material, coolant pump 742 makes current through the input side of heat exchanger 744, reaction tower 720 or 721, the product side of heat exchanger 744, back pressure regulator 755 thus, and is expelled to outlet from this PLPW device.The object of the second cool stream is that the temperature of the biomass material through extracting and reaction tower 720 or 721 is brought down below saturation temperature, thus allows the biomass material of safety taking-up through extracting.Once temperature is enough low, then this PLPW device can be switched and be back to the first cool stream, and can water in emptying reaction tower, take out biomass material through extracting, and load fresh bio raw material for extracting next time.

It is pointed out that those skilled in the art can regulate and/or change the option of each equipment disclosed herein to obtain the PLPW device comprising at least two reaction towers, wherein each tower has the pipeline infrastructure be connected with at least one water source of supply, one or more heater or heat exchanger are to be heated to about 50 DEG C of-Yue 65 DEG C by described water, about 50 DEG C of-Yue 85 DEG C, about 50 DEG C of-Yue 100 DEG C, about 50 DEG C of-Yue 125 DEG C, about 55 DEG C of-Yue 150 DEG C, about 55 DEG C of-Yue 175 DEG C, about 55 DEG C of-Yue 185 DEG C, about 55 DEG C of-Yue 195 DEG C, about 55 DEG C of-Yue 205 DEG C, about 55 DEG C of-Yue 225 DEG C, about 55 DEG C of-Yue 250 DEG C, about 55 DEG C of-Yue 275 DEG C, about 55 DEG C of-Yue 300 DEG C, about 55 DEG C of-Yue 325 DEG C, about 55 DEG C of-Yue 350 DEG C, about 55 DEG C of-Yue 375 DEG C, about 55 DEG C of-Yue 400 DEG C and be in the temperature of period, and be about 500psi for described water is forced into about 100psi-, about 125psi-is about 450psi, about 150psi-is about 400psi, about 165psi-is about 375psi, about 175psi-is about 350psi, about 175psi-is about 325psi, about 175psi-is about 300psi, about 175psi-is about 275psi, about 175psi-is about 250psi, about 175psi-is about 225psi and is in the pump of period.

PLPW device disclosed herein can be configured with two reaction towers, and each tower is communicated with the single pressurized water source shown in Fig. 8, pressurized heat water source and the cooling water source that pressurizes respectively.Or described PLPW device can be configured with three reaction towers, four reaction towers, five reaction towers, six reaction towers, seven reaction towers, eight reaction towers, nine reaction towers, ten reaction towers.Be in the scope of the invention provide in addition pressurized water source for subsequent use, pressurized heat water source and pressurization cooling water source.

Described PLPW device can additionally comprise for receive wherein and process each initial heating stream, liquid flooding stream, add hot-fluid and cool stream during the water equipment for purifying of wastewater streams of discharging from reaction tower, then by treated water recycle to liquid flooding stream, during to add in hot-fluid and cool stream one or more strands of.

Exemplary PLPW device disclosed herein is suitable for extracting from biomass material and reclaiming component, described biomass material is such as lignocellulosic material, as pulp, vegetable, skin slag, root timber material, vegetable material, timber, stalk, careless material, seed, nut, powder, bagasse etc.Described exemplary PLPW device is also suitable for extracting from non-plant organisms material and reclaiming component, and described non-plant organisms material is such as algae bio matter, fish meal etc.

Embodiment

embodiment 1:PLPW process wheat stalk

Research disclosed in this embodiment uses the reaction tower of two kinds of different PLPW throughflow type reactor assemblies and three kinds of different scales.All connectors, annex, pipe, valve and container by corrosion-resistant and be designed for 13.1MPa (1900psi) the highest operating pressure at 250 DEG C stainless steel form.

At the PLPW reaction system 800 (Fig. 9) of indoor structure bench scale, it comprises: water source of supply 805, high speed liquid chromatography (HPLC) pump 810 (Waters 515 model, Milford, MA), temperature controlled baking oven 815 (model 851F, Fisher Scientific, Pittsburgh, PA), 2.0m [external diameter is the stainless steel tube of 3.2mm (1/8 ")] preheating coiled pipe 820, reaction tower 825, 1.0m cooling worm 830 (external diameter is the stainless steel tube of 3.2mm (1/8 ")), there is back pressure regulator 835 (the Upchurch Scientific of 5.2MPa (750psi) cylinder, Oak Harbor, WA) to keep the pressure in this system, with collection container 840.Also between preheating coiled pipe 820 and reaction tower 825, provide pressure-reducing valve 822.Use stainless steel tube (external diameter 3.2mm (1/8 ")) and connector carry out connection device part (that is, HPLC pump, reaction tower and back pressure regulator).

PLPW reaction system 900 (Figure 10) is used to run iodine tower, and in indoor based on the design construction pilot-scale reaction tower of bench scale system (Fig. 9).For all tests, by regulating back pressure regulator 950 (Tescom, Elk River, MN) under making the pressure in described system remain on 11MPa (1500psi).To pressurize from the distilled water in cistern 910 and use measuring pump 915 (model P300, Wanner Engineering Inc., Minneapolis, MN) with constant flow rate pumping, measuring pump 915 has pulsation damper 920 (the Wanner EngineeringInc. be arranged on after pump 915, Minneapolis, MN, USA) to guarantee the steady flow in this system.Within the system, pipe-in-pipe heat exchanger 925 (Exergy LLC, Garden City, NY, USA) realizes two tasks: (i) the first, and heat exchanger 925 to cool after reaction tower 935 and is being expelled to the solvent before collection container 955; (ii) the second, by from discharge in solvent the heat removed pass to enter immersion heater 930 (ASBHeating Elements Ltd., Bethridge, ON, CA) before enter solvent.In this way, water described in heat exchanger 925 preheating reduce the energy requirement of this system.Pressure-reducing valve 945 is provided between heat exchanger 925 and immersion heater 930.Use stainless steel tube (external diameter 12.7mm (1/2 ")) and connector so that the equipment part except iodine tower is linked together, described iodine tower is connected with the system of the pipe with 6.35mm (1/4 ") external diameter.

By stainless steel tube (1.27cm (1/2 ") external diameter; 1.0cm internal diameter × 10cm length) build bench scale reaction tower 825 (Fig. 9) and hold annex (Chromatographic Specialties Inc; Brockville; ON, CA) capping with chromatograph-Ta.Iodine tower 935 amplifies (table 7) by bench scale device with 5 times.Described device is the 5cm internal diameter × 50cm length (MODcol being provided with steel flange, MandelScientific Company Inc., Guelph, ON, CA) reaction tower, it is with graphite o shape sealing ring and the sealing of stainless steel end plate, by its tapping to be connected with described PLPW reaction system.Described pilot-scale reaction tower is the steel flange tower (Enterprise Steel Fabricators Ltd., Kelowna, BC, CA) of customization, and it amplifies 3.56 times (Fig. 7) relative to described amplifying device.End corrosion resistant plate and the sealing ring capping of o shape also seal, and tapping is to be connected with described PLPW reaction system.When not in use, the remainder of described amplifying device and pilot-scale device and PLPW reaction system separates by valve.Because the material of described amplification scale and pilot-scale reaction tower increases, they are equipped with band heater 940 (ASB Heating Elements Ltd., Bethridge, ON, CA) to contribute to heating and to maintain tower temperature.

Table 7

^aequivalent apparent speed in tower is 1.27 × 10 ^-3m/s,

^bwherein length is the bed degree of depth.

Except the size of iodine tower, be also suitably exaggerated experimental condition (table 7).To these test temperature of selection 165 DEG C and the solvent of 60mL/g: solid ratio.Selection comprises 1.27 × 10 ^-3the apparent speed of m/s, this corresponds respectively to bench scale reaction tower, iodine tower and pilot-scale reaction tower 6mL/ minute, the flow rate of 150mL/ minute and 1900mL/ minute.Keep the identical bed degree of depth and diameter ratio, and regulate sample quality to keep having identical bulk density (and porosity) in each scale tower.To remain in reaction tower to make straw sample and dispersion in order to help lend some impetus to PLPW, with the void volume at stainless steel wool packed column each tower end place, and with 20 μm and 100 μm of stainless steel imitation frosted glass (frit) respectively in the capping of entrance and exit place; Except the pilot-scale device not using stainless steel sinter.

Hydrolysis program by first causing with reaction tower described in water liquid flooding, then by described system heating to test temperature, then keep this temperature sufficiently long time in tower, to reach balance to allow sample temperature, then begin to flow through described reaction tower.Once flowing through described reaction tower, then abandon not containing analyze thing solution first step part (corresponding in described system from reaction tower top to the dead volume of collection container), and collect scheduled volume based on selected solvent: the solution of solid ratio.A part (about 60mL) liquid extract is collected, and to analyze at being stored in 4 DEG C, by the freeze drying at being stored in-20 DEG C together with solid residue of remaining liquid extract, until analyze them by each test.

According to NREL standard analyzer (Hyman etc., 2007, Determination of AcidSoluble Lignin Concentration Curve by UV-Vis Spectroscopy; LaboratoryAnalytical Procedure (LAP).NREL/TP-510-42617; National RenewableLaboratory:Golden, CO, USA; Sluiter etc., 2008, Determination ofStructural Carbondydrates and Lignin in Biomass; Laboratory AnalyticalProcedure (LAP) NREL/TP-510-42618; National Renewable Laboratory:Golden, CO, USA) analyze the structural carbon hydrate of solid residue and cryodesiccated liquid extract, lignin, acetyl group and content of ashes.The insoluble lignin of acid (AIL) and acid accumulator soluble lignin (ASL), by first making sample be hydrolyzed 1 hour with 72% sulfuric acid in a water bath at 30 DEG C, are then diluted to 4% sulfuric acid and press down at 121 DEG C in the glass pressure tube sealed and boil 1 hour and measure.After cellulose and hydrolysis of hemicellulose, analyze AIL by weighing.Under 320nm, the ASL in hydrolysate is measured by AAS (Sluiter etc.).Use 30L g ^-1cm ^-1absorptivity so that extinction reading is changed into mass value.The lignin content result of sample is reported with AIL and ASL sum, and to protein content correction.

Structural carbohydrate, cellulose (glucose) and hemicellulose (wood sugar, galactolipin, arabinose and mannose) use the Agilent 1100 (AgilentTechnologies being equipped with RI-detector by HPLC, Palo Alto, CA) by hydrolysate quantitative assay.Described HPLC analyze be used in operation at 75 DEG C there is deliming filter cylinder (Bio-Rad Laboratories, Hercules, CA) hPX-87P post (300 × 7.8mm) (AMINEX is the registration mark of Bio-Rad LaboratoriesCorp., Hercules, CA, USA) carries out.Described HPLC system is by with Agilent the G1329A Autosampler that Plus software (CHEMSTATION is Agilent TechnologiesInc., Santa Clara, the registration mark of CA, USA) controls and G1312A induction system composition.The HPLC level filtered water that use flow rate is 0.5mL/ minute as mobile phase, and for each sample, is automatically injected the aliquot that 50 μ L filter in advance.According to the method that (2008) such as Sluiter instruct, by contrasting with one group of known sugared standard specimen and use the concentration of sugared recovery coefficient absorption measurement carbohydrate.

The method that acetyl group, formic acid and levulic acid are instructed according to (2008) such as Sluiter; Agilent 1100 (the Agilent Technologies being equipped with RI-detector is used by HPLC; PaloAlto, CA) by hydrolysate quantitative assay.Described HPLC analysis is used in the cation H that has of operation at 55 DEG C and refills the Bio-rad filtering post (30 × 4.6mm, Bio-Rad Laboratories, Hercules, CA) hPX-87H post (300 × 7.8mm, Bio-Rad Laboratories, Hercules, Ca) also uses flow rate for 0.6mL/ minute 0.005M H ₂sO ₄mobile phase carries out.

Method (2002, the Colorimetricdetermination of Hexuronic acids in plant materials.Anal.Chem.51:936-941) quantitative assay that uronic acid in hydrolysate is instructed according to Scott.The aliquot (0.125mL) of described hydrolysate is added into the 0.125mL 2%NaCl-3%H be in test tube ₃bO ₃in solution.In ice bath, by dense H ₂sO ₄to be added in test tube and to mix.Then, described test tube is heated 40 minutes in a water bath at 70 DEG C.Then, take out test tube and be also cooled to room temperature, in reactant, then add 1% of 0.1mL be in MX in glacial acetic acid.After 10 minutes, by the absorbance under 400nm and 450nm being averaged and the calibration curve of itself and D-glucuronic acid (Sigma-Aldrich Co., St.Louis, MO) being contrasted and measures uronic acid concentration.

The content of ashes of solid is by being equipped with temperature controller (Furnatrol II 413 series by sample, Thermolyne Corporation, Dubuque, IA) Muffle furnace (model F-A1730, Thermolyne Corporation, Dubuque, IA) in burn completely and measure.Described temperature controller is set as rising to 105 DEG C from room temperature, keeps 12 minutes, rises to 250 DEG C with 10 DEG C/min, keeps 30 minutes, rises to 575 DEG C with 20 DEG C/min, keeps 180 minutes, is down to 105 DEG C and keeps until sample removes.Residuum in crucible is taken as content of ashes.

Protein content uses AOAC Official Method 997.09 (2008, Nitrogen inbeer, wort, and brewing grains, protein (total) by calculation, AOACInternational) in disclosed method estimated by nitrogen content.Before analysis, solid residue is ground with the Unloading sieve by 0.5mm in hammer-mill (MF 10, IKA-Werke GmbH & Co.KG, Staufen, Germany).Before analysis, by sample in vacuum drying oven at 60 DEG C dried overnight.Nitrogen content by burning the sample of drying and using Leco FP-528 blood urea/nitrogen analyzer (Leco Corporation, St.Joseph, MI) to measure at 850 DEG C.Nitrogen calibration curve uses ethylenediamine tetra-acetic acid (EDTA) and corn flour (Leco Corporation, St.Joseph, MI) to obtain.Protein content is by being multiplied by the coefficient of 6.25 by nitrogen content (%) and estimating.

With in calcium carbonate and liquid extract, filter through 0.20 μm of injection filter, and measure carbohydrate monomer for direct HPLC.Then, by getting the concentration calculating carbohydrate oligomer through hydrolysis total carbohydrates content and the difference of content of monomer that recorded by liquid sample recorded by cryodesiccated extract.Catabolite 5-hydroxy-2-methyl furfural (HMF) and furfural are measured by using DAD to detect direct HPLC mensuration by same sample.

SigmaStat30 (version 3 .5, Systat Software, Inc., Point Richmond, CA, USA) is used to analyze data.Using the impact of ANOVA process analysis reactor scale, when finding there are differences, testing by Tukey the value contrast that is averaged.The difference of p≤0.05 is regarded as significantly.

Before enforcement hydrothermal treatment consists, first measure the composition (table 8) of natural straw.Composition analysis use natural straw material-not as described in NREL laboratory procedure with water and alcohol extract to remove the material of extract.

Table 8

* average? standard deviation, n=4

^※to protein correction

mass balance:

After hydrothermal treatment consists, the mass balance of wheat stalk and the reaction tower good agreement (table 9) of all scales.The loss of amplifying device is the highest, is 7.67%; The loss of bench scale is minimum.The total soluble matter material of 26-40% and the remaining solid residue of 57-72% are in (the total soluble matter material of 13-56% and the remaining solid residue of 40-77%) (Mok etc. within the scope reported other crops through throughflow type PLPW hydrothermal treatment consists in document, 1992, Uncatalysed solvolysis of whole BiomassHemicellulose by hot compressed liquid water.Ind.Eng.Chem.Res.31:1157-1161).

Table 9

* there is in row the mean value significantly different (p < 0.05) of different Superscript letters

Calculate with initial substance-solid residue-vehicle substance

, between amplification system and pilot-scale system, there is not significant difference (p>0.05) in the inventory just through being hydrolyzed and extract or the residue amount aspect remained in reaction tower.In bench scale system, less material is hydrolyzed and extracts, thus in reaction tower, leave the residue of much bigger amount.Theoretically speaking, if device suitably amplifies, then should not produce difference due to the size of reaction tower in extraction.But hydrothermal treatment consists is not only a kind of solvation and is extracted phenomenon, but also relates to the chemical reaction of the carbohydrate inversion form in living beings.Be hydrolyzed, make carbohydrate polymer be ruptured by addition hydrone thus.Described reaction there is time dependence and a certain amount of ion existing for experience to carry out water ionization and acid produces, and additionally can be subject to the impact of any solubility restriction of discharged compound.In these three factors, the time of staying of hydrothermal treatment consists is the factor that in these tests, different tower scale uniquely changes.There is in reaction tower equal solvent: solid compares and under apparent speed, for bench scale, the time of collecting the solvent of aequum is less than 10 minutes; For amplification scale, 48 minutes; For pilot-scale, 170 minutes.10 minute processing time in bench scale tower may be not enough to hydrolysis is fully completed.

the composition of solid residue and liquid fraction:

By in the reaction tower of three scales with PLPW hydrothermal treatment consists CPS wheat stalk obtain solid residue and provide in table 10 forming of liquid fraction.Analyze in pilot-scale the solid residue (Figure 11 (A), 11 (B), 11 (C)) with the bed degree of depth with different composition.By the results averaged (table 10) of the solid residue composition of pilot-scale reaction tower under the different bed degree of depth.

With regard to the composition of solid residue and liquid fraction, there are differences (table 10) hardly between amplification system and pilot-scale system.Different piece between described two kinds of scales is only the xylan content of solid residue and the lignin content of liquid fraction.The xylan content amplified in tower is slightly low, and lignin content in liquid fraction is higher.Except the higher lignin in liquid fraction, the lower xylan in residue expects the combination that obtains because lignin and cellulose and hemicellulose bonding, thus with its formation complex.Lignin plays the fender effect around hemicellulose, and limits the contact of hydrolytic process medium and hemicellulose.Remove the raising permission more residue hemicellulose contact to the lignin amount in liquid extract, and the amount that raising is hydrolyzed by hydrothermal treatment consists and extracts.Amplifying in tower the possible cause that the lignin that improves extracts is compared with pilot-scale tower, higher and more uniform temperature distribution during startup.Pilot-scale tower comprises much more thermal material, and this material is difficult to when running this device heat and can has buffering effect to any temperature fluctuation during operation.In addition, large flange and capping play large thermoreceptor effect on the apparatus.Start flowing when round starts after, pilot-scale reaction tower will expend about 20 minutes just can reach operating temperature, and iodine tower reaches operating temperature in flowing beginning in 1 minute.Be enough to first make the lignin solvation of more vast scale during amplifying this short time high temperature in tower and make more substantial hemicellulose be exposed to be hydrolyzed.The higher catabolite HMF amplified in tower is also the indication that treatment temperature raises compared with other scale systems with the concentration of furfural and the xylo-oligosaccharide concentration of reduction.

The solid residue of bench scale system and the composition of liquid fraction are similar to amplification and pilot-scale system, wherein only there is minority Main Differences.The beta-dextran content of solid residue is less than bench scale system by almost 25%, this is because xylan content is than the height in other devices almost three times.This conforms to this thinking of insufficient hydrolysis caused due to the short processing time, and matches (table 9) with the minimizing of the dissolving material of bench scale reaction tower.Higher acetyl content in the solid residue of bench scale system also shows during hydrothermal treatment consists, has the hydrolysis of reduction due to the minimizing of acetic acid generation.The liquid fraction of bench scale reaction tower is also containing more arabinooligosaccharides and mannose monosaccharide, and the concentration of wood sugar monose is lower.The structure of araban makes it extremely sensitive to hydrolysis, and therefore the reservation (table 10) of araban in solid residue and the reservation of oligosaccharides in liquid fraction also show the time of staying owing to reducing, this process so harshness.This also takes temperature out from the low catabolite furfural liquid fraction.

Table 10

There is significant difference (p < 0.05) in the mean value * in row with different Superscript letters

^※to protein correction

Although there is a small amount of significant difference between the composition of these three kinds of scale reaction towers, still there are differences in the composition of more extensive reaction tower.Measure three kinds of main component celluloses, hemicellulose and lignins change with the bed degree of depth of the solid residue in pilot-scale system.Cellulose is reported with the beta-dextran content of solid residue, and hemicellulose (it is the branching polysaccharide be made up of pentose (D-wood sugar and Arabinose) and hexose (D-galactolipin, D-Glucose and D-MANNOSE)) is reported with the summation of the xylan in solid residue, galactan, araban and mannosan.The bottom of reaction tower is to top from pilot-scale, and content of cellulose reduces almost 15% (Figure 11 (A)).In three sections, the top of described reaction tower, the content of hemicellulose does not have difference (Figure 11 (B)).Only in the bottom stage of described tower, the content of hemicellulose is lower, although this difference only a little higher than 1%.This can be partly due to the lower lignin content in described reaction tower bottom stage, which thereby enhances the accessibility (Figure 11 (C)) of cellulose to hydrolysis.

The top of reaction tower is to top from pilot-scale, and the lignin content of solid residue is almost double.The solubility of known lignin is subject to the extreme influence of solvent property.The solvability of PLPW is the highest bottom (it enters in reaction tower herein).Lignin in the stalk located bottom described reaction tower PLPW due to upwards become by this tower saturated before easily solvation.Therefore, compared with top, more lignin solvation in the lower section of reaction tower.Lignin is solvation in pilot-scale device, but to extract than amplifying the lower amount of tower, this can find out (table 10) from the lower lignin content liquid fraction.

Liu etc. (2003, The Effect of Flow Rate of Compressed Hot Water onXylan, Lignin and Total Mass Removal from Corn Stover.Ind.Eng.Chem.Res.42:5409-5416) propose a kind of lignin solvation mechanism, lignin and self reacting with other compounds whereby, thus formed can because long residence time or reaction temperature reduce the larger molecule of precipitation.The material demand dissolved is about the time of 3.5 times by pilot-scale reaction tower than with identical apparent speed by amplifying tower.In bottom stage, the lignin of solvation is upwards by this tower.When the lignin of solvation and other lignins and compound react, it forms larger molecule and is also settled out from PLPW.Before discharge reaction tower, these molecules containing lignin can be deposited in upper segment, and the lignin content explaining solid residue thus improves this phenomenon.

the recovery of carbohydrate and non-carbohydrate product:

From wheat stalk, reclaim carbohydrate and non-carbohydrate product be not subject to the very large impact (Figure 12 (A), 12 (B)) that reaction tower amplifies.For all tower scales, in the recovery of glucose or the recovery of a small amount of hemicellulose carbohydrate-galactolipin, arabinose and mannose, do not observe difference (Figure 12 (A)).Pilot-scale device produces about 26g wood sugar/kg dry straw (Figure 12 (A)) more than amplifying device.But the solid residue of these two kinds of scales gives the residual xylan of identical amount.Amplify tower and reach operating temperature more fasterly than pilot-scale reaction tower, therefore produce furfural due to the higher temperature in the hydrothermal treatment consists starting stage, wood sugar produces and may there are differences.Under 39% gross production rate of liquid fraction, the xylose production 30g/kg dry straw lower than amplifying device of bench scale device, 56g/kg dry straw lower than pilot-scale device.Residual xylan in solid residue goes out more than 3 times than other scale reaction tower heights, and remains the potential xylan of 40%.Therefore, caused by insufficient hydrolysis that this difference mainly causes due to the time of staying of deficiency.

Lignin in iodine tower extracts than almost 50% (Figure 12 (B)) of the height in bench scale and pilot-scale reaction tower.The reduction that in bench scale reaction tower, lignin is produced may be the accessory substance of insufficient hydrolysis.Remain in lignin in solid residue than the height in iodine tower and pilot-scale reaction tower almost 25%.Amplifying the difference that the lignin between pilot-scale tower produces is cause the time of staying of improving, instead of caused by the flow distribution in the difference of solvation or this two towers.In pilot-scale reaction tower, lignin modified and cause some lignins to precipitate before taking out from reaction tower with the reaction of himself or other compounds.This result in the axial gradient of lignin concentration in this tower, and this also makes the real lignin content being difficult to all residual solids that accurate Calculation is obtained by hydrothermal treatment consists.Due to the tower scale for the production of residue non-carbohydrate component, there is difference (Figure 12 (B)) slightly.

The sign of natural CPS wheat stalk makes to calculate the productive rate obtained by PLPW hydrothermal treatment consists.Productive rate calculates divided by the potential group component in described natural straw with the group component collected in liquid extract, and reports with percentage.To amplify and the productive rate curve of three kinds of main component-celluloses of lignin fiber cellulosic biomass of pilot-scale tower, hemicellulose (wood sugar, galactolipin, arabinose and mannose sum) and lignin is plotted in Figure 13 (A), 13 (B), 13 (C).From bench scale system, do not obtain productive rate curve, this is because the material extracted during hydrothermal treatment consists is not enough to carry out multiple spot analysis.This is a major defect of minimum scale systems, and indicates and why need to amplify these methods to make to understand described dynamics better.

In glucose yield, there is not the difference because reaction tower scale causes, and overall production rate keeps lower (Figure 13 (A)).Hemicellulose productive rate in amplification tower is lower than pilot-scale tower, although hemicellulose fluctuation much bigger (Figure 13 (B)) in amplification tower.The productive rate amplified in tower and pilot-scale tower reaches 55% and 66% of potential hemicellulose in former CPS wheat stalk respectively.When starting hydrothermal treatment consists almost 20%, the dynamics of described reaction keeps identical, the deviation of dynamics generation thereafter and productive rate starts deviation.As mentioned above, the hemicellulose residual quantity in solid residue is identical; Therefore in the reaction tower of two kinds of scales, the hemicellulose of equal quantities is hydrolyzed.Between different scales, the deviation of productive rate is because in iodine tower, the degraded of hemicellulose causes.The lignin productive rate very different (Figure 13 (C)) of described two kinds of scale reaction towers.Gross production rate and the initial extraction speed of iodine tower are much higher.The lignin productive rate of iodine tower and pilot-scale reaction tower reaches 43% and 32% of potential lignin in CPS wheat stalk respectively.With regard to lignin is produced, the lignin productive rate of the reduction in larger pilot scale scale reaction tower is the time of staying of the raising caused due to amplification procedure, causes the reaction of lignin in described reactor and modification to cause thus.

In these researchs, the successful amplification of CPS wheat stalk hydrothermal treatment consists has obtained only exists very other solid residue of community and liquid fraction at composition and yield aspects.The lignin amount aspect that difference mostly appears at xylan hydrolysis degree and extracts.Be the extraction system of the leading phenomenon of technique for solubility and mass transfer, the key that container amplifies keeps identical apparent speed and solvent: solid ratio.Solubility factor is introduced in this technique by the hydrothermal treatment consists of lignin fiber cellulosic biomass, but is also subject to the control of Chemical Kinetics.In this experiment, compare with pilot-scale reaction tower with iodine tower, bench scale reaction tower causes the insufficient hydrolysis of hemicellulose fraction.Compared with amplification tower, lignin in pilot-scale tower extracts insufficient, and this may be caused by it precipitates in described reaction tower before removing at lignin.In the system introducing reaction factor (as hydrothermal treatment consists), the time of staying becomes important.In the amplification of reaction tower, apparent speed must be kept, this is because inside and outside mass transfer plays a secondary role in kinetics (it depends on the time of staying).For the amplification of the hydrothermal process equipment in future, answer the apparent speed in adjusting tower (flow rate) to make the time of staying equal.Reaction tower heat drying is contributed to the hemicellulose productive rate improving stalk.

The PLPW process of embodiment 2:Concord grape skin

The grape skin produced by the commercially available fruit juice production of Concord grape autumn in 2011 is provided by business fruit company.After receiving grape skin, by forced convection baking oven (model 40AF, Quincy Lab Inc., Chicago, IL, USA) at 75 DEG C dried overnight and measure its moisture.Remaining grape skin deep cooling at-20 DEG C is stored until need to process.

At five temperature (85 DEG C, 120 DEG C, 150 DEG C, 175 DEG C), use the single flow rate of 10mL/ minute and the solvent of 30mL/g: solid ratio bench scale PLPW system (Fig. 9) processes grape skin.In addition, at 120 DEG C, three-wheeled operation is carried out to determine the change degree of extraction process.The grape skin of 8 batches is amounted to the process of bench scale system.The optimal treatment condition determined is 120 DEG C and 7.5mL/g solvent: solid ratio, and used as processing the operating condition of grape skin by pilot-scale PLPW system (Figure 10).

With the grape skin of pilot-scale system process 7 batches.In addition, the solvent with 22.5mL/g: the treatment conditions process two batches of solid ratio adds batch and and takes turns, collected total 15 fractions to determine phenols and the anthocyanin wash-out with the processing time further every 5-10 minute.The grape skin of 9 batches is amounted to the process of pilot-scale system.

bench scale extracts:

Show by by batch data gathered of bench scale system process, the dry of extraction increases (table 7) with the rising for the treatment of temperature.For the complete round of 30mL/g, the dry substance concentration in the liquid extract at 175 DEG C is than four at 85 DEG C times taller (being respectively 0.86%, 0.21%).Obtained dry productive rate at this represents 175 DEG C is the obtained dry productive rate at 23.1%, 85 DEG C is 6.2%.But most of dry extracts in round at first 7.5mL/g and extracts.Therefore, the most only enforcement first 7.5mL/g extraction, makes productive rate reasonably high thus and production concentration in liquid extract is in highest level.

Under the treatment temperature of 150 DEG C and 175 DEG C, extract loses its distinctive purple and becomes significant brown, and has smell of burning, thus obtains undesirable product.The phenols content of the extract at 150 DEG C and 175 DEG C is high, but required anthocyanin disappears (Figure 14 (A), 14 (B)) due to high temperature from extract.For remaining 85 DEG C and 120 DEG C for the treatment of temperatures, at 120 DEG C, obtain the highest total phenols productive rate and content, at 85 DEG C, obtain the highest anthocyanin productive rate and content (table 11).In general, at 120 DEG C, obtain the best of breed of concentration and productive rate.

From the extraction of collecting under the treatment temperature of 120 DEG C, the total phenolic concentration in the dried extract of all fractions is 9.05%, this represent in skin slag can obtain phenols 114.6% productive rate.In PLPW, reaction treatment grape skin provides phenols more more than the phenols that can obtain from untreated skin slag.For all fractions that 120 DEG C are extracted, the anthocyanin concentration in extract is 0.36%, and this represents the productive rate of 19.4%.

pilot-scale extracts:

The grape skin of 10 batches is processed by pilot-scale PLPW system (Fig. 8) to obtain 1500L (400 gallons) extract at 120 DEG C.Analyzing two groups of extractions-the first group is 70L, under maximum extracted concentration (7.5mL/g); Second group is 750L, under maximum yield (22.5mL/g solvent: solid ratio)-and to evaluate the evaporation economy of liquid extract.

What pilot-scale PLPW extracted the results are summarized in table 12.At 7.5mL/g solvent: under solid ratio, the average dry substance concentration in liquid extract and productive rate are respectively 1.0% and 7.6%.Total phenolic concentration average out to 12.9% in dried extract, this represent the productive rate that can obtain phenols in the grape skin of 96.0%.Anthocyanin concentration average out to 1.1% in dried extract, this represent the productive rate that can obtain anthocyanin in the grape skin of 33.7%.One batch obtains the dry matter content lower than other rounds and productive rate, this is because caused by some by-pass flows of tower middle sleeve.The round in all future all does this correction.To another batch, the heat time after chuck is heated to temperature was down to 0 hour by 1 hour.Compared with other rounds, dry productive rate or concentration do not change.Total phenols productive rate is slightly low, but concentration in dry extracts is identical with other rounds.But, the anthocyanin productive rate in dried extract and concentration difference high 59% and 85%.This may be cause owing to not using the heating period anthocyanin degraded at elevated temperatures lower caused by.

At 22.5mL/g solvent: under solid ratio, the average dry substance concentration in liquid extract and productive rate are respectively 0.56% and 12.5% (table 12).Total phenolic concentration average out to 11.7% in dried extract, this represents the productive rate that can obtain phenols in the grape skin of 108.1%.Anthocyanin concentration average out to 1.07% in dry extracts, this represents the productive rate that can obtain anthocyanin in the grape skin of 49.9%.Total phenols in dry extracts and anthocyanin concentration and short and long round similar.But under 7.5mL/g, productive rate increases with extraction, and cost is the dry substance concentration in liquid extract.

For C2 round on February 1 (see table 12), productive rate and the concentration of dry, total phenols and anthocyanin are maximum (tables 13) in the commitment extracted.Clearly, after 7.5mL/g sample, the products collection efficiency subsequently in fraction reduces (table 13) greatly.And the production of extracting compound in fraction does not subsequently increase (Figure 15).Therefore, the solvent extended to more than 7.5mL/g will be extracted: this comparatively Zao observation that the benefit of solid ratio acquisition is less is correct.

At 7.5mL/g solvent: solid extracts grape skin than lower PLPW and obtains the productive rate that 96.0% can obtain phenolic compound, its concentration in extract is 12.9%; With the anthocyanin productive rate in the parent material of 33.7%, its concentration in extract is 1.10% (table 12).At 12.3mL/g solvent: solid extracts than lower interval the obtained phenolic compound productive rate that grape skin obtains 62.8%, its concentration in extract is 8.64%; With the anthocyanin productive rate in the parent material of 61.4%, its concentration in extract is 1.98% (table 12).Compared with interval hot water extracting technology, described PLPW technology obtains the phenols of many 40% with the concentration of 1.5 times.In addition, described PLPW system employs the water that suitable industrial hot water extracts half, and this substantial saving in for removing water to obtain the evaporation cost of dried extract.

the impact of scale:

By tower diameter is increased to 20.3cm (Fig. 8) from 2.2cm, bench scale PLPW system (Fig. 9) is amplified.The remainder of tower and extraction system parameter are amplified based on 9 times and suitably amplify, and keep two extractors to have equal sample bulk density and the time of staying (table 14) simultaneously.

The major part of whole dry and polyphenol extract in first 30% (7.5mL/g solvent: solid ratio) of this extraction, this represent 76% and 72% total solids (table 15) in bench scale and pilot-scale system.Meanwhile, there is phenolic concentration in the dry of extraction.Initial Concord grape skin has total phenols content of 0.94%, and this is concentrated into 8.98-14.26% (table 15) in the dry of bench scale system and pilot-scale system.

Table 14

^bwherein length is the bed degree of depth

The time of staying=the bed degree of depth/apparent speed

Extraction time=volume/flow rate of collection

Significant difference (p >=0.05) is there is not in the amount of substance extracted by bench scale or pilot-scale system.In theory, if device amplifies suitably, then should there is not the extraction difference because reactor size causes.But PLPW extracts and solvation not only occurs and extracts phenomenon, but also the chemical reaction relevant to temperature and time occurs, and is combined with the decomposition of living beings in described PLPW system.Therefore, in total phenolic concentration of liquid extract, there is the significant difference (p≤0.05) relevant to scale.Tartrate and flavonols concentration not there are differences (p >=0.05), but in anthocyanin concentration, different PLPW extraction system exists significant difference (p≤0.05).Pilot-scale PLPW system creates the anthocyanin doubling bench scale PLPW system quantities.This may be caused by the difference due to reaction tower size and heating schedule.In bench scale PLPW system, the liquid flooding of described tower hot water and this tower heat 45 minutes in an oven with under guaranteeing that raw material and tower are all in Extracting temperature.In pilot-scale PLPW system, chuck is made to reach Extracting temperature with tower described in hot water liquid flooding, then by this system heating 60 minutes.

Although pilot-scale PLPW system has the longer heat time due to larger tower diameter, but the time heating that the material demand of tower center is longer.Therefore, the material heating of pilot-scale tower center wants much slow, and degree of heat will lower than the material in much smaller bench scale tower.Known anthocyanin is to responsive to temperature (Mazza etc., 1993, Anthocyanins in Fruits, Vegetables, and Grains; CRC Press:Boca Raton, FL), therefore they more easily decompose due to the time of staying under high temperature and disappear in bench scale tower.

Embodiment 3: the PLPW process of mossberry skin slag

The mossberry skin slag produced by commercially available fruit juice production autumn in 2012 is provided by business fruit process company.After receiving mossberry skin slag, by measuring its moisture in the middle dried overnight of forced convection oven (model 40AF, Quincy Lab Inc., Chicago, IL) at 75 DEG C.Remaining mossberry skin slag deep cooling at-20 DEG C is stored until need to process.

At six temperature (85 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C), bench scale PLPW system (Fig. 9) is used to process mossberry skin slag.The most active solvent of determined Concord grape skin in embodiment 2: solid than being 7.5mL/g, therefore by same solvent: solid extracts than being used for mossberry skin slag.Heat time is set as within 15 minutes, decompose and loss to prevent the phytochemical in extract.

Use the biomass material of other types and use the time of staying (bench scale flow rate is 10L/ minute) that the previous research and design of pilot-scale system (Fig. 8) is used for keeping the time of staying in pilot-scale reaction tower to equal in bench scale reaction tower, the enough high to such an extent as to living beings flow resistance that is that cause due to the mossberry skin slag degree of depth in this tower of 8mL/ minute flow rate in pilot-scale reaction tower is enough to cause bed to cave in, and causes tower to block thus.If find the flow rate in pilot-scale PLPW system to be down to 4L/ minute (this corresponds to 5mL/ minute flow rate of bench scale system), then blocking will not be problem.In order to measure the impact of flow rate on extraction process, at 85 DEG C and 120 DEG C, in bench scale system, run two kinds of flow rate 5mL/ minute and 10mL/ minute.

In pilot-scale PLPW system (Fig. 8), run 7 tests, thus determine that optimum extraction temperature is 120 DEG C.Due to the dry matter concentration in the liquid extract of bench scale round, by solvent in pilot test system: solid ratio rises to 8.5mL/g.Subsequently, with the mossberry skin slag of pilot-scale PLPW system process 7 batches.

Use Glories method (1979, Reserches sur la matiere colorante des vinsrouges.Bull.Cim.9:649-2655) improvement version measure the phenols content of mossberry skin slag, and measure dry extract as mentioned below.With 3% formic acid be in methyl alcohol by Sample Dilution 2 times, the acid methyl alcohol of 50% (50%MeOH, 1.5% formic acid, 48.5% water) is then used to dilute 5-50 doubly.Make each solution whirling motion and leave standstill about 15 minutes, then using spectrophotometer (DU-65, BeckmanInstruments Inc., Fullerton, CA) to read its absorbance under 280nm, 320nm, 360nm and 520nm.Use the absorbance (A) under 280nm to estimate total phenols, use the A under 320nm to estimate tartrate, use the A under 360nm to estimate flavonols, use the A under 520nm to evaluate anthocyanin.The standard specimen used to total phenols is gallic acid, and paratartaric acid ester standard specimen used is caffeic acid, the standard specimen used to flavonols is quercetin, and the standard specimen used to anthocyanin is C-3-G.All standard specimens are all prepared in acid methyl alcohol.All standard specimens are all available from Sigma-Aldrich (Oakville, ON).

According to the instruction (1985 of Porter etc., The conversion of procyanidins andprodelphinidins to cyanidin and delphinidin.Phytochem.25:223-230), use the procyanidin content that sour butanols determination method is determined in former mossberry skin slag and dried extract.The sample of Powder Extract is dissolved in 70% methyl alcohol of 30mL.Add dense HCl and the 10mL water of 15mL wherein.By each solution return 80mL, then cool and use 70% methanol dilution to 250mL.50mL solution is evaporated to about 3mL in rotary evaporator (Rotovapor-R, B ü chi, Switzerland), and content is transferred in separatory funnel, wash flask with water and be added in described funnel.In separatory funnel, add butanols, and rock content to be separated organic layer.Collect OPC fraction and be adjusted to 100mL with butanols.Absorbance under using spectrophotometer (DU-65, Beckman Instruments Inc., Fullerton, CA) to measure 545nm, described procyanidin content is expressed as cyaniding chloride.

The moisture of mossberry skin slag is higher than grape skin (being respectively 64%, 46%).This higher water content makes to be difficult in tower, fill as many mossberry skin residue material, thus causes compared with grape skin, and the extract volume that every round is produced is lower.In bench scale PLPW system, run mossberry skin slag specimen product do not have problems.But in pilot-scale PLPW system, mossberry skin slag ratio grape skin is more prone to blocking, therefore must close supervision flow rate.

bench scale extracts:

The process of flow rate on mossberry skin slag has remarkable impact (table 16).Compared with the flow rate of 5mL/ minute, the dry under the higher flow rate of 10mL/ minute and the productive rate of OPC and concentration all lower.But, under the flow rate of 5mL/ minute, total phenols productive rate and concentration lower.Flow rate in change system also can affect the time of staying of extract in tower.Under the flow rate of 5mL/ minute, the time of staying was than 10mL/ minute flow rate high twice.The raising of the time of staying allowed before extract is discharged and cooled, and had the more time to react in this tower in PLPW.When OPC, the time of staying of raising allows larger insoluble oligomer and polymer molecule to resolve into less and more easily molten form.But the longer time of staying can make other heat sensitive phenols decompose.Therefore, at lower flow rates, OPC productive rate can improve, and total phenols productive rate can reduce due to degradation reaction.

In bench scale PLPW system, the dry of extraction increases (table 11) with the rising for the treatment of temperature.At 150 DEG C, the dry substance concentration in liquid extract is the twice at 85 DEG C many (being respectively 2.00%, 0.78%).This represents the obtained dry productive rate of 15.38% (150 DEG C) and 5.88% (85 DEG C).

Result shows that flow rate was increased to by 5mL/ minute and within 10mL/ minute, makes the productive rate of dry and OPC reduce 10-20%.The phenolic concentration of extract is at 120 DEG C and 130 DEG C the highest (table 16), but required anthocyanin disappears (Figure 16 (A), 16 (B)) at higher than the temperature of 110 DEG C from extract.Because the course of reaction of mossberry skin slag in PLPW provides the more phenols than obtaining from untreated skin slag, therefore total phenols productive rate is higher than 100%.OPC maximum concentration in dry extracts obtains under the treatment temperature of 120 DEG C.At 120 DEG C, the procyanidin concentration in dry extracts is 2.88%, and this represents in the mossberry skin slag of 31.55% can obtain OPC productive rate.In general, the concentration of phenols and OPC and the best of breed of productive rate obtain under the treatment temperature of 120 DEG C.

pilot-scale extracts:

Condition pilot-scale PLPW system (Fig. 8) optimized is used to process the mossberry skin slag of 7 batches, thus obtained 630L extract (table 17).Except round 3, in general, the fluctuation on described Iarge-scale system between each round is little.The by-pass flow problem of sleeve can be produced in round 3, but show its result for contrast object.Average dry substance concentration in liquid extract is 1.26%, thus obtains the obtained dry productive rate of 10.9%, this identical with bench scale system (concentration and productive rate are respectively 1.21% and 9.2%).The quality of the extract of pilot-scale PLPW system is better than with those of bench scale PLPW system recoveries.Chromatogram under the 520nm obtained by bench scale PLPW system shows, and higher than at the temperature of 110 DEG C, anthocyanin disappears (Figure 17 (A), 17 (B)) substantially from the extract of drying.The pilot-scale PLPW system run at 120 DEG C creates the dried extract had with bench scale PLPW system Anthocyanin content like 85 DEG C and 110 DEG C of lower classes.Procyanidin concentration average out to 3.50% in the dried extract of pilot-scale PLPW system, this represents the obtained OPC productive rate in the mossberry skin slag of 45.5%, and this is significantly better than with bench scale PLPW system recoveries (it has the procyanidin concentration and productive rate that are respectively 2.88% and 31.55%) (table 16).Total phenols content of described two systems is similar with productive rate.

The pilot-scale PLPW of mossberry skin slag obtains the obtained OPC productive rate (table 17) of 45.5% under being extracted in 3.50% concentration in extract.Intermittent fever water extraction only obtains the obtained OPC productive rate (table 16) of 19.5% under being taken at 1.21% concentration in dried extract.The OPC of many 133% is obtained under the concentration of described PLPW technology in the dried extract being almost three times in interval hot water extracting technology.In addition, pilot-scale PLPW system uses the skin slag processing identical amount than the water of the few half of interval hot water extracting.Very expensive except anhydrating from extract, and described technique is the technique that dried extract production cost is the highest.This can save industrial cost greatly when attempting producing dried extract to use the reduction of this water consumption of PLPW extractive technique to show.

Lower flow rate and the time of staying of raising are favourable to extracting OPC from mossberry skin slag.Compared with the research previously carried out with Concord grape skin, at the temperature of 120 DEG C, obtain maximum output and the concentration of OPC with denseer liquid extract.Therefore, the temperature of described pilot-scale PLPW system at 120 DEG C, the larger solvent of 4L/ minute (being equivalent to the 5mL/ minute of bench scale system) and 8.5mL/g: solid is than lower operation.

Embodiment 4: the PLPW process of cannabigerol

Corase grind cannabigerol is provided by the commodity production business of cannabis oil.Sample is worn into the uniform powder had compared with coarsegrain.By measuring the moisture of cannabigerol at 75 DEG C in the middle dried overnight of forced convection oven (Model 40AF, Quincy Lab Inc., Chicago, IL).Remaining cannabigerol deep cooling at-20 DEG C is stored until need test.

Use bench scale PLPW system (Fig. 9) to implement two and extract round.Subsequently, the round that enforcement two is extra under different set condition.In both cases, described bench scale tower is all mounted with cannabigerol and with the water liquid flooding of 35 DEG C.

In first constant temperature round, after tower liquid flooding, do not stopping through 10 minutes, temperature being risen to 70 DEG C under flowing.Implement the remainder (table 18) of this extraction as in the foregoing embodiment.The flow rate of bench scale PLPW extraction system remains 5mL/ minute and uses the total solvent of 30mL/g: solid ratio, comprises intensification fraction.

Table 18

Implement two warm round with extract more material and or (i) obtains more protein in extract, or (ii) purification residue is to improve its protein content (table 19).After this tower liquid flooding, do not stopping through 10 minutes, temperature being risen to 70 DEG C under flowing.Rose to 120 DEG C before through 10 minutes by 70 DEG C in temperature, at 70 DEG C, collect two kinds of fractions.Residue fraction (table 19) is collected under constant 120 DEG C of Extracting temperature.The flow rate of bench scale PLPW extraction system remains 5mL/ minute, and uses the total solvent of 30mL/g: solid ratio, comprises intensification fraction.

Table 19

Corase grind cannabigerol has the starting protein content of about 35% and the lipoid of 10%, and the surplus of described dry comprises carbohydrate and inorganic matter.

The protein analysis of cryodesiccated extract is undertaken by independently third-party analysis.Fraction is grouped as follows:

Round 1 (70 DEG C of constant temperature):

Residue (70/05/30GCHM 2013/06/06 residue)

Fraction 1 (70/05/30GCHM 2013/06/06F1)

Fraction 2 and 3 (the 70/05/30GCHM 2013/06/06F2 of combination; 70/05/30GCHM2013/06/06F3)

Fraction 4,5,6 and 7 (the 70/05/30GCHM 2013/06/06F4 of combination; 70/05/30GCHM2013/06/06F5; 70/05/30GCHM 2013/06/06F6; 70/05/30GCHM2013/06/06F7)

Round 2 (two sections 70 DEG C/120 DEG C):

Residue (70-120/05/30GCHM 2013/06/06 residue)

Fraction 1 (70-120/05/30GCHM 2013/06/06F1)

Fraction 2 and 3 (the 70-120/05/30GCHM 2013/06/06F2 of combination; 70-120/05/30GCHM2013/06/06F3)

Fraction 4,5,6 and 7 (the 70-120/05/30GCHM 2013/06/06F4 of combination; 70-120/05/30GCHM 2013/06/06F5; 70-120/05/30GCHM 2013/06/06F6; 70-120/05/30GCHM 2013/06/06F7)

It is pointed out that under 80 DEG C or higher temperature, the protein in cannabigerol can boiling as albumen, thus forms solid matter in extraction column, blocks this system subsequently.By test determine: if (i) keeps after this tower liquid flooding flow and (ii) keeps Extracting temperature lower than 80 DEG C, then protein can not solidify lower extraction, and this tower can not block.

Table 20

^aassuming that there is 35% protein in former dry initial substance

^bthe mean value of fraction 2 and 3

^cthe mean value of fraction 4,5,6 and 7

Described extraction performance shows, milky white thing has appearred in the extract due to fraction 2-4, and protein is completely solvated and removes from living beings.In constant temperature round, described PLPW is extracted in liquid extract the initial substance obtaining 20.1%, and in two sections of rounds, obtain the initial substance (table 20) of 25.5% in liquid extract.

In 70 DEG C of constant temperature extract, in fraction 2 and 3, obtain the highest protein concentration and productive rate (table 20).In extracting at two sections 70 DEG C/120 DEG C, because extraction scheme is identical with constant temperature round, therefore first three fraction is not analyzed.PLPW when determining that the rising of temperature is extracted on most of water soluble protein to rear four fraction analyses extracts the impact of back segment.Protein yields in two sections of fraction 4-7 extracted is slightly high, is 11.65%, but concentration in dry extracts is slightly low, is 46.47%.

These results show, cannabigerol can comprise the water soluble protein extracted by PLPW of significant quantity.Successful runs under 70 DEG C of constant temperature in dried extract 77.74% maximum concentration under give 36% protein yields.Subsequently, complete two sections of rounds, thus after most of ease of solubility material extracts from cannabigerol, treatment temperature is risen to 120 DEG C.This causes the better protein yields in dried extract, but nearly 49% of starting protein still remains in residue.Although a large amount of protein residues is in residue, this protein obviously can be different from the protein of extraction.

Embodiment 5:PLPW process parsley is to extract apiin (apigenin-7-(2-O-celery glycosyl glucoside)

Dehydration parsley sheet derives from the commercial supplier of the U.S..After receiving described material, by measuring its moisture in the middle dried overnight of forced convection oven (model 40AF, Quincy Lab Inc., Chicago, IL) at 75 DEG C.Remaining parsley sheet deep cooling at-20 DEG C is stored until need to process.

With the parsley sheet of bench scale PLPW system (Fig. 9) process through dehydration.Parsley of dewatering (18.5g, dry weight and do not grind) is filled to be had in the stainless steel extraction column (22cm length × 2.2cm internal diameter) of frit at two ends.This extraction process is started to reach the pressure of 300psi by being pumped in bench scale PLPW system by water with the flow rate of 5mL/ minute.After being heated 15 minutes by this tower, at 110 DEG C, 120 DEG C and 130 DEG C, water is pumped across this system.Collect four kinds of fractions (F1, F2, F3 and F4) of parsley extract at each temperature and freeze drying.Use MeOH-H ₂o (2:1, volume ratio) extracts the methods analyst phenolic compound that cryodesiccated sample is instructed to use Luthria (2006).

For composition analysis, parsley slice lapping is made it by standard screen (425 μm) to prepare fine grained.10mL MeOH-H is used in ultrasonic device ₂o (2:1, volume ratio) extracts about 0.250mg ground sample and reaches 30 minutes.After extraction, by centrifugal for sample (10,000rpm) 15 minutes, and by supernatant collection in 25mL volumetric flask.The extra 10mL MeOH solution with re-suspension of residue is also extracted again.Described supernatant and first time extract are merged, cumulative volume is complemented to 25mL.By the aliquot (1mL) of the extract of merging again 9, under 000rpm centrifugal 15 minutes to remove any residual particle, and for the instruction (2006, A systematic approach for extraction ofphenolic compounds using parsley (Petroselinum crispum) flakes as amodel substrate.J.Sci.Food Agric.86:1350-1358) according to Luthria etc. by Folin-Ciocalteus (FC) method and HPLC methods analyst phenols content.The HPLC of parsley extract analyzes use and is connected with the serial HPLC of Agilent HP 1100 (Agilent Technologies, Waldbronn, Germany) of software, binary high-pressure pump, vacuum degassing machine and light emitting diode matrix detector carries out.All chromatographic isolation all Luna RP C-18 ( 150 × 3mm) post uses guard column (C-18,4 × 2mm) (PHENOMENEX is the registration mark of Phenomenex, Torrance, CA, USA) carries out.Post oven temperature is 30 DEG C.Gradient system is made up of 5% formic acid (A) and methyl alcohol (B): 30%MeOH isocratic elution 5 minutes, then rose to 100%MeOH through 21 minutes, keeps 5 minutes under 100%MeOH.Diode array is used to detect apiin (under 270nm).

Pure apiin (>=93.9%) standard specimen is purchased from ChromaDex (Santa Ana, CA, USA).5 milligrams of standard specimens are dissolved in 10mL methanol-water (2:1, stock solution); Other dilutions are prepared by being diluted in methanol-water by described stock solution.The regression equation of apiin (under 270nm) and coefficient (R2) are y=47515x-149.19 (R ²=0.9999,0.23-0.02mg/mL).

The water content of former dehydration parsley is 5.5%.The solvent be made up of MeOH-water (2:1) is successfully used to extract apiin from grinding parsley sheet and extract for PLPW.Use the existence of apiin in pure external standard identification parsley extract and estimate.The representative chromatogram of pure apiin standard specimen is shown in Figure 18 (A), and the representative chromatogram of the extract of dry parsley is shown in Figure 18 (B).The main peaks identified in parsley extract is apiin, its retention time (12.4 minutes) is associated with commercially available standard specimen with UV spectrum, thus confirms identification and the purity at peak.The apiin concentration in sample is estimated by drawing the linear regression line (concentration is plotted in x-axis, and peak area is plotted in y-axis) of pure apiin standard specimen.Apiin regression equation under 270nm is y=47515x-149.19 (R ²=0.9999).Apiin content in parsley raw extract and TP are respectively 2.65% and 1.78%.

At three kinds of different desired temperatures (110 DEG C, 120 DEG C and 130 DEG C) and constant liquid: solid ratio (30mL/g), flow rate (5mL/ minute), pressure (300psi) and extract parsley by PLPW under extraction time (111 minutes).The data summarization comprising extraction conditions, dry productive rate and phenols composition of the parsley obtained by PLPW is in table 21.The column bleed that described PLPW extraction system is very well extracted parsley and do not resulted in blockage or depress at constant-pressure pump.The color of the fraction first of PLPW extract is bright yellow, and this may be caused by beta carotene existing in parsley and zeaxanthin.At a 7.5mL/g solvent: the dry obtaining higher amount under solid ratio.The maximum amount total solids of 11.6g has been reclaimed by the treatment temperatures of 120 DEG C.Apiin by the main peak of parsley PLPW extract identification.By adding pure apiin standard specimen in parsley extract, to compose with the UV of published technical report and retention time contrasts and identifies this compound.The first fraction (Figure 19 (B)) under 120 DEG C of desired temperatures gives apiin (7.7%) and the TP (3.3%) of maximum amount, and wherein dry matter content is 9.96g.Based on these results, treatment temperature have impact on the extraction of parsley dry.At 110 DEG C, polarity (Figure 19 (A)), solvent can have impact to the diffusion coefficient of sample matrices, the lower extractability of thermal response on apiin, and under 130 DEG C (Figure 19 (C)), part apiin is degraded due to higher temperature.

Embodiment 6: the PLPW process of root of Rhodiola sachalinensis

Dry root of Rhodiola sachalinensis is provided by Advanced Orthomolecular Research Inc. (Calgary, AB, CA).Sample is quite thick, and it has different distribution of particles and caking, but does not grind or cut off before extraction.By measuring the water content of root of Rhodiola sachalinensis at 75 DEG C in the middle dried overnight of forced convection oven (model 40AF, Quincy LabInc., Chicago, IL).The water content of the rhodiola root living beings recorded is 3.4%.Remaining rhodiola root is stored at-20 DEG C until need to test.

Three Extracting temperature (110 DEG C, 130 DEG C, 150 DEG C) are tested to the root of Rhodiola sachalinensis of bench scale PLPW system process.Use the solvent of 30mL/g: solid ratio, and the fraction each volume of extract being divided into 4 7.5mL/g solvents.Flow rate is remained 5mL/ minute, will be set as the heat time decomposing in extraction to prevent phytochemical and losing for 15 minutes.Extraction column is filled with 15g material.

the analysis of extract and raw material:

Rhodiola root dry extracts sample is fully dissolved in the methyl alcohol of 70% with the concentration of 10mg/mL.Clarified by the centrifugal sample that makes, and the supernatant of 20 μ L is injected on LC/MS device.Sample is run twice.In order to contrast, be dissolved in 40mL 70% methyl alcohol by 2g being extracted sample and to analyze an extraction sample with 70% methanol dilution (10mg root/mL) 1:5.Signal is by retention time identification, and rhodioside (salidroside), rhodioloside (rhodioloside), Luo Saiyin, Rosavin (rosavin), rosin use the gradient HPLC being connected with DAD absorbance detection be separated acquisition and verified by holotype electrospray ionization mass spectrum with the molecular weight of network plug fixed (rosidrin).The amount of rhodioside, Luo Saiyin, Rosavin and rosin is estimated by contrasting with the pure standard specimen available from ChromaDex (Santa Ana, CA, USA).

In order to analyze rhodioside and Rosavin, develop the method comprised the steps.In order to measure the initial level of root of Rhodiola sachalinensis in primitive root material and Rosavin, use coffee mill by grinding in small, broken bits for the representative sample of root of Rhodiola sachalinensis, then by 80% aqueous methanol with 25mL (20:80, methyl alcohol: water) extraction in ultrasonic 25 minutes.Method (2007, the Simultaneousdetermination of Salidroside and tyrosol in extracts of Rhodiola L.bymicrowave assisted extraction and high-performance liquidchromatography.J.Pharm.Biomed.Anal.45:510-515 instructed according to Mao etc.; Ganzera etc., 2001, Analysis of the Marker Compounds of Rhodiola L. (Golden Root) byReversed Phase High Performance Liquid Chromatography.Chem PharmBull.49:465-467), by extract under 9000rpm at room temperature centrifugal 15 minutes, and inject 10 μ L supernatants and analyze root of Rhodiola sachalinensis and Rosavin content with HPLC.The standard specimen of rhodioside and Rosavin is purchased from Sigma-Aldrich (Sigma-Aldrich, St Louis, MO, USA).Each standard specimen of 2.5mg is dissolved in 80% aqueous methanol (stock solution) of 10mL.Other dilutions are prepared by diluting described stock solution in 80% aqueous methanol.The regression equation of rhodioside (under 278nm) and Rosavin (under 250nm) and coefficient (R2) are y=2693.1x-11.727 (R ²=0.9983, to 0.023mg/mL) and y=82174x-89.367 (R ²=0.9995,0.035-0.0125mg/mL).

Cryodesiccated PLPW root of Rhodiola sachalinensis extract sample is extracted to carry out HPLC analysis as described above by 80% aqueous methanol of 25mL.Compound analysis uses and is connected with (CHEMSTATION is Agilent Technologies Inc.Santa Clara to software, CA, the registration mark of USA), the serial HPLC of AgilentHP 1100 (the Agilent Technologies of binary high-pressure pump, vacuum degassing machine and light emitting diode matrix detector, Waldbronn, Germany) carry out.All chromatographic isolation all Luna RP C-18 ( 150 × 3mm) post uses guard column (C-18,4 × 2mm) (PHENOMENEX is the registration mark of Phenomenex, Torrance, CA, USA) carries out.Post oven temperature is 30 DEG C.Gradient system is made up of water (A) and methyl alcohol (B): 20%A isocratic elution 25 minutes, then rose to 90%A through 15 minutes, keeps 10 minutes under 90%A.Use Diode Array Detector rhodioside (under 278nm) and Rosavin (under 250nm).Peak by n-compound to be added in gadol extract, contrast UV spectrum and retention time and identify.

The initial substance productive rate (Figure 20) of 48% is obtained under described 1.7% concentration be extracted at 110 DEG C in liquid extract.At 130 DEG C, under 1.7% concentration in liquid extract, obtain the initial substance productive rate (Figure 20) of 52%.At 150 DEG C, under 2.1% concentration in liquid extract, obtain the initial substance productive rate (Figure 20) of 60%.The fraction (which represent the solvent of 15mL/g: solid ratio) that the first two is collected comprises the abundantest dry productive rate.

HPLC/DAD analyze result show, Rosavin (Luo Saiyin, Rosavin and rosin sum) and the concentration of rhodioside the highest under 130 DEG C for the treatment of temperatures, this represents the extract (table 22) of 0.79% and 0.62% respectively.The peak of Luo Saiyin, Rosavin, rosin and rhodioside identifies in Figure 21 (A)-21 (C).The content (Figure 22 (A)-22 (C)) of these compounds in dry PLPW extract extracts content (Figure 23 (A)-23 (C)) lower than the methyl alcohol of initial root of Rhodiola sachalinensis material.The low rhodioside of PLPW extract and Rosavin content may be due to large quantity of material generation solvation and extract caused by.In the complete water soluble of described sample, but comprise the material be insoluble in 70% methyl alcohol of significant quantity.This insoluble fraction may be carbohydrate, and it can not extract effectively in water-ol is extracted, but can extract in PLPW system.These carbohydrates mainly PLPW extract in reduce rhodioside and Rosavin concentration caused by.

Table 22

The method (2007) of instructing according to Mao etc. analyzes former root of Rhodiola sachalinensis living beings and dry PLPW extract, thus makes to calculate productive rate (table 24).The result of Rosavin with is obtained by independently commercial laboratory those quite, but Determination of Salidroside doubles the value that commercial laboratory is reported.Data in table 23 are added test by standard and are confirmed.The method of Mao etc. (2007) is exclusively used in rhodioside, and compared with the method used with commercial laboratory, described method is more responsive to described compound.PLPW obtains the highest rhodioside and Rosavin concentration and productive rate in the first two fraction under being extracted in the Extracting temperature of 130 DEG C.Rhodioside productive rate in the first two fraction is almost 100%, and the concentration in dried extract is 1.5%, that is out the specification of root of Rhodiola sachalinensis extract.Rosavin productive rate in the first two fraction is almost 85%, but the concentration in dried extract is only 0.65%, and this is lower than 3% to root of Rhodiola sachalinensis extract defined.Therefore, in the obtained rhodioside extracted in rhodiola root and Rosavin effectively, but it is nonselective extracting method to described PLPW, and concentration in dried extract is low.Under the Extracting temperature of 150 DEG C, due to the degradation that higher temperature causes, the productive rate of rhodioside and Rosavin reduces, although dry productive rate improves.

Table 23

Claims (15)

1., for using the device adding and force down polar water and extract from biomass material and reclaim component, it comprises:

Two or more reaction towers, each tower respectively with following members: the source of supply of the water that (i) heats, (ii) the pressure (hydraulic) water source of supply heated, and the pressure (hydraulic) water source of supply that (iii) cools, each tower has the outlet for discharging liquid product stream;

For the pump by described each reaction tower pressurization;

The multiple valves cooperated separately with described reaction tower and described pump for: described each reaction tower is forced into selected pressure by (iv), (v) pressure selected by described each reaction tower is kept selected by time, and the pressure in each compressive reaction tower described in (vi) release; With

For accepting the collection container from the liquid product stream of described each tower at described each tower pressure dwell.

2. device according to claim 1, additionally comprises one or more for receiving and the water treatment facilities of purification waste water stream wherein.

3. device according to claim 2, is additionally comprised for being regulated and the device of the water of process through purifying by one or more heating and pH.

4. device according to claim 3, additionally comprises the cistern for storing the water of a part through purifying.

5. device according to claim 1, additionally comprises the cistern for storing a part of wastewater streams.

6. device according to claim 1, additionally comprises one or more collection container for accepting the liquid product stream from described each tower successively wherein at described each tower pressure dwell.

7. device according to claim 1, the water source of supply wherein heated comprises the pipeline infrastructure be communicated with back pressure regulator with water source, at least one heat exchanger, at least one heater and forces down polar water for also producing to add with each reaction tower described in hot water liquid flooding.

8. device according to claim 1, the source of supply of the water wherein heated comprises the pipeline infrastructure be communicated with back pressure regulator with water source, at least one heat exchanger, at least one heater and is heated to selected temperature for by described each reaction tower.

9. device according to claim 1, the pressure (hydraulic) water source of supply wherein heated comprises the pipeline infrastructure be communicated with back pressure regulator with water source, at least one heat exchanger, at least one heater and forces down polar water Continuous Flow through described each reaction tower for making adding of heat, and described 3rd pipeline infrastructure is additionally communicated with described collection container.

10. device according to claim 1, the pressure (hydraulic) water source of supply wherein cooled comprises the pipeline infrastructure be communicated with back pressure regulator with water source, at least one heat exchanger, at least one heater and is cooled to selected temperature for by described each reaction tower.

11. devices according to claim 1, additionally comprise and two or more reaction towers, the source of supply of the water of heating, the pressure (hydraulic) water source of supply of heating, the pressure (hydraulic) water source of supply of cooling, automation control system for being communicated with multiple valve by the pump of described each reaction tower pressurization controllably imports successively for by current: (i) and water source, at least one heat exchanger, first pipeline infrastructure of the low polar water for also producing pressurization with each reaction tower described in hot water liquid flooding that at least one heater is communicated with back pressure regulator, and water source (ii), at least one heat exchanger, the second pipe infrastructure for described each reaction tower being heated to selected temperature that at least one heater is communicated with back pressure regulator, and water source (iii), at least one heat exchanger, at least one heater be communicated with back pressure regulator for making adding and forcing down three pipeline infrastructure of polar water Continuous Flow through described each reaction tower of heat, described 3rd pipeline infrastructure is additionally communicated with described collection container, (iv) and water source, at least one heat exchanger, the 4th pipeline infrastructure for described each reaction tower being cooled to selected temperature that at least one heater is communicated with back pressure regulator.

12. devices according to claim 11, wherein said automation control system is programmable.

13. devices according to claim 11, wherein said automation control system can manual operation.

14. devices according to claim 11, additionally comprise with the pressure (hydraulic) water source of supply of the pressure (hydraulic) water source of supply of the source of supply of the water of two or more reaction towers, heating, heating, cooling, for pump that described each reaction tower is pressurizeed with multiple for manual control system current controllably being imported successively the first pipeline infrastructure, second pipe infrastructure, the 3rd pipeline infrastructure are communicated with the valve of the 4th pipeline infrastructure.

15. device according to claim 1, additionally comprise the container for receiving the wastewater streams of discharging from described each reaction tower after described each tower decompression.